ES2714130T3 - Detergent composition - Google Patents

Abstract

A phosphate-free dishwashing detergent composition in unit dose form having a weight of 8 to 25 grams, the composition comprising: i) more than 5 to 8 grams of an organic complexing agent selected from the group consisting of methylglycinate acid, its salts and derivatives thereof, N, N-diacetic glutamic acid, its salts and derivatives thereof, iminodisuccinic acid, its salts and derivatives thereof, carboxymethylinulin, its salts and derivatives thereof, and mixtures thereof; ii) a dispersing polymer; iii) 1 to 3 grams of bleach and wherein the complexing agent and the dispersing polymer are in a weight ratio of 10: 1 to 20: 1.

Description

DESCRIPTION

Detergent composition

Technical field

The present invention relates to the cleaning sector. It refers to a cleaning product, in particular a phosphate-free detergent dishwashing composition comprising a high level of a complexing agent and a low level of a polymer. The composition provides good cleaning, finishing, care and presents a good environmental profile.

Background of the invention

Dishwashing detergents in unit dose form are becoming increasingly popular. One of the restrictions of the products in unit dose form is that they have a limited volume determined by the size of the product dispenser in the dishwasher, limiting the amount of active substance that the detergent may contain. Traditionally, dishwashing detergents were phosphate type; However, due to environmental problems, the use of phosphate is avoided.

The dishwashing detergent formulator is continuously looking for ways to improve the performance and environmental profile of detergent compositions. Sometimes, there are negative interactions between the ingredients of the products and / or during washing, for example, high levels of complexing agents can have a negative impact on the performance of enzymes, in particular on the performance of proteases.

Baked, burned, and bleachable stains are among the most difficult soils and stains to remove. The dishwashing detergent should not only provide a good cleaning, but also a good finish (absence of film and stain formation and provide shine) and care.

US-2010/0041575 A1 proposes a way to formulate phosphate-free detergents; however, the cleanliness provided by the compositions of US-2010/0041575 can be further improved.

The aim of the present invention is to provide a dishwashing detergent composition with a good environmental profile that provides: i) good cleaning, even difficult to remove stains such as baked, burned, and bleachable stains, ii) good finish, that is, leaving items washed without films or stains and shiny, and iii) good care, especially of glass objects that are prone to deterioration during dishwashing and avoid the formation of stains on stainless steel items.

Summary of the invention

According to the first aspect of the invention, a phosphate-free dishwashing detergent composition is provided. By "phosphate free" is meant herein that the composition comprises less than 1%, preferably, less than 0.1% by weight of the phosphate composition. The composition comprises bleach, a high level of complexing agent and a low level of polymer. The composition provides a good cleaning, which includes: i) the removal of bleachable spots, in particular tea spots; ii) the removal of protein dirt, especially stains containing egg and meat; iii) the removal of baked, burned spots. The composition also provides good shine, preventing the formation of films and spots. It also provides good care, especially avoiding the formation of a colored film on stainless steel items. The composition is compatible with the environment due to the biodegradability of the complexing agent and the low level of polymer used.

The composition of the invention is in the form of a unit dose. By "unit dose form" it is understood herein that the composition is provided in a form sufficient to provide enough detergent for washing. Suitable unit dosage forms include pills, sachets, capsules, bags, etc. For use herein, compositions in unit dose form wrapped in water soluble material, for example polyvinyl alcohol, are preferred. Especially preferred are compositions in unit dose form wrapped in a polyvinyl alcohol film having a thickness of less than 100 pm. The detergent composition of the invention weighs from 8 to 25 grams, preferably from about 10 to about 20 grams. This weight range fits comfortably in a dishwasher dispenser. Even if this range involves a low amount of detergent, the detergent has been formulated so as to provide all the advantages mentioned hereinbefore.

The composition of the invention comprises a high level of an organic complexing agent. This comprises more than 5, preferably more than 5.8 and especially the same or more than 6 to 8 grams of complexing agent. For the purposes of this invention, a "complexing agent" is a compound capable of bonding polyvalent ions such as calcium, magnesium, lead, copper, zinc, cadmium, mercury, manganese, iron, aluminum and other cationic polyvalent ions to form a complex. soluble in water. The complexing agent has a stability constant Logarithmic ([log K]) for Ca2 of at least 5, preferably at least 6. The stability constant, log K is measured in an ionic strength solution of 0.1, at a temperature of 25 ° C.

The complexing agent is selected from the group consisting of methyl-glycine-diacetic acid, its salts and derivatives thereof, glutamic-N, N-diacetic acid (N, N-diacetic glutamic acid - GLDA), its salts and derivatives thereof, iminodisuccinic acid (iminodisuccinic acid - IDS), its salts and derivatives thereof, carboxymethylinulin, its salts and derivatives and mixtures thereof. An especially preferred complexing agent for use herein is selected from the group consisting of MGDA and salts thereof, especially preferred for use herein is the MGDA trisodium salt.

The composition of the invention also comprises a dispersing polymer. A dispersing polymer is a polymer capable of: i) dispersing inorganic salts such as those derived from the hardness of water and detergent ingredients such as carbonate; and / or ii) disperse organic food waste found in dirty dishes.

For the purposes of this invention, the term "crockery" encompasses tableware and kitchen utensils and everything usually washed in a dishwasher.

The complexing agent and polymer are in a weight ratio of 10: 1 to 20: 1, more preferably from about 12: 1 to about 18: 1. Surprisingly, it has been found that the compositions with this relationship provide good cleaning, lack of film formation and a lack of unexpectedly improved spot formation.

Preferably, the dispersing polymer is selected from the group consisting of alkoxylated polyalkyleneimines, polymeric polycarboxylates, including alkoxylated polycarboxylates, polymers of unsaturated monomeric acids, polyethylene glycols, styrene copolymers, cellulose sulfate esters, carboxylated polysaccharides, sulfonated copolymer polymers mixtures thereof. Preferably the dispersing polymer is a sulfonated polymer. For the purposes of the present invention, a "sulfonated polymer" is a polymer that comprises sulfur in any of its forms. The "sulfonated polymer" of the invention preferably comprises carboxyl groups. Preferably, the complexing agent is the trisodium salt of MGDA and the dispersing agent is a sulfonated polymer, which more preferably comprises 2-acrylamido-2-methylpropanesulfonic acid, monomer.

It has been observed that some phosphate-free dishwashing compositions may leave a colored film on stainless steel items. This problem is improved or even avoided when the composition of the invention is free of citrate.

It has also been observed that compositions comprising a high level of complexing agents can negatively affect the yield of enzymes, in particular the yield of proteases and if the level of complexing agent is higher, the yield of amylase can also be affected. negatively. It has been surprisingly discovered that the composition of the invention provides very good removal of protein stains.

Preferably, the composition of the invention comprises a low level of a crystalline growth inhibitor, more preferably, 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP).

Preferably, the composition of the invention has a pH of 9 to 12, more preferably about 10 to about 11.5, measured in a 1% aqueous solution by weight / volume in distilled water at 20 ° C. Preferably the composition of the present invention has a reserve alkalinity of 10 or higher, preferably 12 or higher, most preferably 14 or higher. "Alkalinity reserve" herein refers to the ability of a dishwasher composition to maintain an alkaline pH in the presence of acid. This is related to the ability of a dishwasher composition to have enough reserve alkali to treat any added acid - from water and / or tableware - maintaining the pH. More specifically, it is defined as the grams of NaOH per 100 cc, with a pH greater than 9.5, in a product. The alkalinity reserve of a solution is determined as follows.

A pH meter (for example an Orion model 720A) is calibrated with an Ag / AgCl electrode (for example a safe flow electrode Orion model 9172BN) using standard 7 and pH 10 buffer buffers. A 1% solution is prepared of the composition to be analyzed in distilled water. Sample weight is noted. The pH of the solution is measured at 1% and the solution is titrated volumetrically at a pH of 9.5 using a 0.2 N HCL solution. The alkalinity reserve (RA) is calculated as follows:

Reserve alkalinity =% NaOH x relative density.

% NaOH = ml HCl x Normality of HClx4 '/ weight of the sample aliquot valued volumetrically * Equivalent weight of NaOH in the equation of% NaOH,

derived from:

% NaOH = ml HCl x Normal HCl x Equiv. NaOH weight x 100/1000 x sample aliquot weight volumetrically

Cleaning using hard water is especially a challenge. According to a second aspect of the invention there is provided a method for dishwashing dishwashing using the composition of the invention. Even in hard water conditions, the composition of the invention provides very good cleaning, finishing and care results. By "hard water" is meant herein water having a hardness equal to or greater than 100 ppm, preferably 200 ppm and especially 300 ppm of CaCO ³ .

According to a third aspect of the invention, the use of the composition of the invention is provided to remove stains containing proteins, in particular stains containing eggs and / or milk in hard water.

The elements of the composition of the invention described with respect to the first aspect of the invention are applied, changing what is necessary, to the second and third aspects of the invention.

Summary of the invention

The present invention encompasses a dishwashing detergent composition. The composition comprises a high level of an organic complexing agent (preferably an MGDA salt, more preferably the trisodium salt), a low level of polymer (preferably a sulfonated polymer, more preferably a sulfonated polymer comprising 2-acrylamido acid monomers) 2-methylpropanesulfonic) and bleach (preferably sodium percarbonate). The composition provides excellent cleaning, finishing, care and does not harm the environment. A method for dishwashing in dishwashers is also provided using the composition of the invention and a method for dishwashing in dishwashing in hard water. The composition behaves really well even in hard water conditions. The invention also encompasses the use of the composition, preferably in hard water, to remove stains containing proteins, preferably egg dirt and milk.

Unit dose form

The composition of the invention is presented as a unit dose. Products in unit dose form include pills, capsules, sachets, bags, injection molded containers, etc. Preferably, the composition is in a container made of water soluble material. Preferred packages are bags, where the detergent composition is coated by a water soluble film and injection molded containers, wherein the detergent composition is placed in a container of water soluble material manufactured by injection molding. Both the detergent composition and the wrapping material are soluble in water. They dissolve easily when exposed to water in a dishwashing process, preferably during the main wash. The package may have a single compartment or a plurality of compartments. The compartments may comprise a composition in liquid or solid form.

Preferably, the unit dose detergent may be in the form of a multi-compartment container. By "multi-compartment package" is meant herein a package that has at least two compartments, preferably at least three compartments, where each compartment contains a composition surrounded by a wrapping material, preferably polyvinyl alcohol. The compartments can be in any geometric arrangement. The different compartments may be adjacent to each other, preferably being in contact with each other. Especially preferred configurations for use herein include overlapping compartments (i.e. one on top of the other), face-to-face compartments, etc. From the point of view of the adjustment of the dishwasher dispenser, the stability and the reduction of the wrapping material, multi-compartment bags or packages having some overlapping compartments and / or some parallel compartments are especially preferred.

Wraparound material

The wrapping material is soluble in water. "Water soluble" means herein that the material has a water solubility of at least 50%, preferably at least 75% or even at least 95%, measured by the method described herein using a filter glass with a maximum pore size of 20 micrometers.

50 grams ± 0.1 grams of wrapping material are added in a 400 ml beaker previously weighed and 245 ml ± 1 ml of distilled water. This is vigorously stirred on a magnetic stirrer set at 600 rpm, for 30 minutes at 20 ° C. The mixture is then filtered through a sintered glass filter with folded paper for analysis with a pore size as defined above (max. 20 micrometers). Water is removed from the collected filtrate by any conventional method and the weight of the remaining material is determined (which is the dissolved or dispersed fraction). Then, the% solubility can be calculated.

The wrapping material is any water soluble material capable of enclosing the cleaning composition of the product of the invention. The wrapping material may be a polymer that has been injection molded to Provide a wrap or it can be a movie. Preferably, the wrapping material is polyvinyl alcohol. Preferably, the wrapping material is a water-soluble polyvinyl alcohol film.

The bag can, for example, be obtained by injection molding or by creating compartments using a film. The wrapping material is usually moisture permeable. The bag of the invention is stable even when the wrapping material is moisture permeable. The liquid composition confers stability to the bag, in terms of both interaction between the different compositions and interaction with the surrounding environment.

Preferred substances for manufacturing the wrapping material include polymers, copolymers or derivatives thereof selected from polyvinyl alcohols, polyvinyl pyrrolidone, poly (alkylene oxides), acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, amides of cellulose, polyvinyl acetates, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamide, maleic acid / acrylic acid copolymers, including starch and gelatin polysaccharides, natural gums such as xanthan and carrageenan. More preferably, the polymers are selected from water-soluble acrylate polyacrylates and copolymers, methyl cellulose, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates and most preferably are selected from poly (alkoxy) vinyl copolymers of polyvinyl alcohol and hydroxypropyl methylcellulose (HPMC) and combinations thereof. Polyvinyl alcohol is especially preferred for use herein and even more preferred are polyvinyl alcohol films.

The most preferred wrapping materials are PVA films known as MonoSol M8630, marketed by Kuraray and PVA films with the corresponding solubility and deformability characteristics. Other films suitable for use in the present invention include films known by the commercial reference PT film or the K series of films supplied by Aicello or the VF-HP film supplied by Kuraray.

The wrapping material herein may comprise other additive ingredients other than the polymer or polymer material and water. For example, it may be advantageous to add plasticizers, for example, glycerol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, sorbitol and mixtures thereof. Preferably the wrapping material comprises glycerol as plasticizers. Other useful additives include disintegration aids.

Detergent composition

The detergent composition of the invention is presented in unit dosage form and can be in any physical form including solid, liquid and gel form. The composition of the invention is very suitable for presentation in the form of a multi-compartment package, more particularly a multi-compartment package comprising compartments with compositions in different physical forms, for example, a compartment comprising a solid-shaped composition and another compartment that It comprises a composition in liquid form. The composition is preferably wrapped by a water soluble film such as polyvinyl alcohol. The composition comprises an organic complexing agent, preferably the MGDA trisodium salt, a dispersing polymer, preferably a sulfonated polymer comprising monomers of 2-acrylamido-2 methylpropanesulfonic acid, a bleach, preferably sodium percarbonate, and preferably a detergent builder inorganic, more preferably, carbonate, a bleach activator, a bleach catalyst, protease and amylase enzymes, non-ionic surfactant, a crystalline growth inhibitor, more preferably HEDP. The compositions are preferably free of citrate.

The composition of the invention preferably has a pH measured in an aqueous solution of 1% by weight / volume in distilled water at 20 ° C from about 9 to about 12, more preferably from about 10 to less than about 11.5 and especially of about 10.5 to about 11.5.

The composition of the invention preferably has a reserve alkalinity of about 10 to about 20, more preferably about 12 to about 18 at a pH of 9.5 measured in NaOH with 100 ml of product at 20 ° C.

Complexing agent

A complexing agent is a material capable of sequestering hardness ions, in particular calcium and / or magnesium. The composition of the invention comprises a high level of complexing agent; however, the level should not be too high due to the negative interaction with enzymes. Too high a level may also have associated glass care problems.

The composition of the invention comprises more than about 5 to about 10 grams, preferably more than about 5.5 to about 8 grams, more preferably more than about 5.5 to about 8 grams of a complexing agent. The complexing agent is selected from the group consisting of methylglycinadiacetic acid, its salts and derivatives thereof, glutamic acid-N, N-diacetic acid, its salts and derivatives thereof, iminodisuccinic acid, its salts and derivatives thereof, carboxymethylinulin , its salts and derivatives thereof and mixtures thereof. The especially preferred complexing agent for use herein is an MGDA salt, in particular the trisodium MGDA salt.

Dispersant polymer

The composition of the invention comprises a low level of dispersant polymer, preferably from about 0.1 to about 1, more preferably from about 0.2 to about 0.9 and especially from 0.3 to 0.6 grams, preferably the polymer Dispersant is a sulfonated polymer, more preferably a sulfonated polymer comprising 2-acrylamido-2-methylpropanesulfonic acid monomers and carboxyl monomers.

Polycarboxylate Polymer

For example, a wide variety of modified or unmodified polyacrylates, polyacrylate / maleates or polyacrylate / methacrylates are very useful. It is believed that these polymers are excellent dispersing agents and improve the overall performance of the detergent, especially when used in the composition of the invention.

Suitable polycarboxylate type polymers include polycarboxylate polymers that can have average molecular weights of about 500 Da to about 500,000 Da, or about 1000 Da to about 100,000 Da or even about 3000 Da to about 80,000 Da. Suitable polycarboxylates can be selected from the group comprising polymers comprising acrylic acid such as Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 (BASF GmbH, Ludwigshafen, Germany), Acusol ™ 45N, 480N, 460N and 820 (marketed by Rohm and Haas, Philadelphia, Pennsylvania, USA) polyacrylic acids, such as Acusol ™ 445 and Acusol ™ 420 (marketed by Rohm and Haas, Philadelphia, Pennsylvania, and the U.S.) acrylic / maleic copolymers, such as Acusol ™ 425N and acrylic / methacrylic acid copolymers.

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are useful herein and can provide an additional fat suspension. Chemically, these materials comprise polyacrylates that have an ethoxy side chain for every 7-8 acrylate units. The secondary chains are linked by ester to a "main structure" of polyacrylate to provide a "comb" polymer type structure. The molecular weight may vary, but may be in the range of about 2000 to about 50,000.

Unsaturated monomeric acids that can be polymerized to form suitable dispersing polymers include acrylic acid, maleic acid (or maleic anhydride), smoking acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene malonic acid. The presence of monomeric segments that do not contain carboxylate radicals such as methyl vinyl ether, styrene, ethylene, etc., is appropriate provided that these segments do not constitute more than about 50% by weight of the dispersing polymer.

Acrylamide and acrylate copolymers with a molecular weight of from about 3000 to about 100,000, preferably from about 4000 to about 20,000 and an acrylamide content of less than about 50%, preferably less than about 20% by weight of dispersant polymer can also be used. Most preferably, said dispersant polymer has a molecular weight of about 4000 to about 20,000 and an acrylamide content of about 0% to about 15%, by weight of the polymer.

Sulfonated polymers

Suitable sulfonated polymers described herein may have a weight average molecular weight of less than or equal to about 100,000 Da, preferably less than or equal to about 75,000 Da, more preferably less than or equal to about 50,000 Da, more preferably about 3000 Da to about 50,000 Da, and especially from about 5000 Da to about 45,000 Da.

The sulfonated polymers preferably comprise carboxylic acid monomers and sulfonated monomers. Preferred carboxylic acid monomers include one or more of the following: acrylic acid, maleic acid, itaconic acid, methacrylic acid, or ethoxylated esters of acrylic acids, with acrylic and methacrylic acids being more preferred. Preferred sulfonated monomers include one or more of the following: sodium (meth) allylsulfonate, vinyl sulphonate, sodium phenyl (meth) allylsulfonate, or 2-acrylamido-methylpropanesulfonic acid. Preferred non-ionic monomers include one or more of the following: (meth) methyl acrylate, (meth) ethyl acrylate, (meth) t-butyl acrylate, methyl (meth) acrylamide, ethyl (meth) acrylamide, t- butyl (meth) acrylamide, styrene, or a-methylstyrene.

Especially preferred sulfonated polymers for use herein are those comprising acrylic acid monomers and 2-acrylamido-methylpropanesulfonic acid monomers.

In the polymers, all or some of the carboxylic acid or sulfonic acid groups may be present in neutralized form, that is, the hydrogen atom atom of the carboxylic and / or sulfonic acid group in some or all of the acidic groups may be substituted with metal ions, preferably alkali metal ions and, in particular, with sodium ions.

Preferred commercial polymers include: Alcosperse 240, Aquatreat AR 540 and Aquatreat MPS marketed by Alco Chemical; Acumer 3100, Acumer 2000, Acusol 587G and Acusol 588G marketed by Rohm &Haas; Goodrich IK-798, K-775 and K-797 marketed by BF Goodrich; and ACP 1042 supplied by ISP Technologies Inc. Especially preferred polymers are Acusol 587G and Acusol 588G supplied by Rohm & Haas, Versaflex Si ™ (marketed by Alco Chemical, Tennessee, USA) and those described in USP 5,308,532 and in WO 2005/090541. Suitable styrene copolymers can be selected from the group comprising styrene copolymers with acrylic acid and optionally sulfonate groups, which have average molecular weights in the range of 1000-50,000, or even 2000-10,000 such as those supplied by Alco Chemical Tennessee , USA UU., With the trade names Alcosperse®747 and 729.

Other dispersant polymers useful in the present invention include cellulose sulfate esters such as cellulose sulfate acetate, cellulose sulfate, cellulose hydroxyethyl sulfate, cellulose methyl sulfate, and cellulose hydroxypropyl sulfate. Sodium cellulose sulfate is the polymer of this most preferred group.

Other suitable dispersant polymers are carboxylated polysaccharides, especially starches, celluloses and alginates. Preferred cellulose-derived dispersant polymers are carboxymethyl celluloses.

Another group of acceptable dispersing agents is that of organic dispersing polymers such as polyaspartos. Amphiphilic graft copolymers are useful for use herein. The suitable amphiphilic graft copolymer comprises (i) a main chain of polyethylene glycol; and (ii) at least one pendant moiety selected from polyvinyl acetate, polyvinyl alcohol and mixtures thereof. In other examples, the preferred amphiphilic graft copolymer is Sokalan HP22, supplied by BASF.

Bleach

The composition of the invention preferably comprises 1, preferably 1.2 to 3 and especially 1.5 to 2.5 grams of bleach.

Inorganic and organic bleaches are suitable for use herein. Inorganic bleaches include perhydrated salts such as perborate, percarbonate, perfosphate, persulfate and persilicate salts. Perhydrated inorganic salts are normally alkali metal salts. The inorganic salt of perhydrate can be included as a crystalline solid without any additional protection. Alternatively, the salt may be coated. Suitable coatings include sodium sulfate, sodium carbonate, sodium silicate and mixtures thereof. Such coatings can be applied as a mixture applied to the surface or sequentially in layers.

Alkali metal percarbonates, especially sodium percarbonate, is the preferred bleach for use herein. The percarbonate is incorporated with maximum preference to the products in a coated form that provides stability to the product.

Potassium peroximonopersulfate is another inorganic perhydrated salt useful herein.

Typical organic bleaches are organic peroxyacids, especially diperoxidedecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Monodiperazelaic acid and diperazelaic acid and monodiperbrasilic acid and diperbrasilic acid are also suitable herein. Diacylperoxides and tetracylperoxides, for example, dibenzoyl peroxide and dilauroyl peroxide, are other organic peroxides that can be used in the context of this invention. Other typical organic bleaches include peroxyacids, with concrete examples being alkylperoxyacids and arylperoxyacids. Preferred representatives are (a) peroxybenzoic acid and its substituted ring derivatives, such as alkylperoxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) substituted aliphatic or aliphatic peroxyacids, such as peroxylauric acid, acid peroxystearic acid,--phthalimidoperoxycaproic acid, [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxicaroproic acid, N-nonenylamidoperadipic acid, and N-nonenylamidopersuccinates, and (c) peroxydicarbonic acid, aliphatic carboxylic acid, aliphatic, aliphatic acid, 1,1 1,9-diperoxyazelaic, diperoxisebacic acid, diperoxibrasilic acid, diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N, N-terephthaloyldi (6-aminopercaproic acid).

Bleach Activators

Bleach activators are typically precursors of organic peraids that enhance the bleaching action during washing at temperatures of 60 and below. Bleach activators suitable for use herein include compounds that, under perhydrolysis conditions, provide aliphatic peroxycarboxylic acids preferably having 1 to 12 carbon atoms, in particular 2 to 10 carbon atoms, and / or acid optionally substituted perbenzoic. Suitable substances contain O-acyl and / or N-acyl groups of the number of specified carbon atoms and / or optionally substituted benzoyl groups. Preference is given to polycylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated derivatives of triazine, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycoluryls, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n-NOBS or iso-NOBS), decanoyloxybenzoic acid (DOBA), carboxylic anhydrides, in particular phthalic acyloxy anhydride , in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and also triethylacetyl citrate (TEAC). If present, the composition of the invention comprises 0.1 to 2, preferably 0.2 to 1 gram of bleach activator, preferably TAED.

Bleach Catalyst

The composition herein preferably contains a bleach catalyst, preferably a metal containing bleach catalyst. More preferably, the metal containing bleach catalyst is a bleach catalyst containing a transition metal, especially a bleach catalyst containing manganese or cobalt.

Preferred bleach catalysts for use herein include manganese triazacyclononane and related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe bispyridylamine and related complexes (US-A-5114611); and cobalt (III) pentamine acetate and related complexes (US-A-4810410). A complete description of the bleach catalysts suitable for use herein can be found in WO 99/06521, page 34, line 26 to page 40, line 16.

Manganese bleach catalysts are preferred for use in the composition of the invention. It is an especially preferred catalyst for using in the present invention a dinuclear manganese complex having the general formula:

wherein Mn is manganese which can be individually in the oxidation state III or IV; each x represents a kind of coordination or bridge selected from the group consisting of H2O, O22-, O2-, OH-, HO2-, SH-, S2-,> SO, Cl-, N3-, SCN-, RCOO- , NH2- and NR3, where R = H, alkyl or aryl, (optionally substituted); L is a ligand, which is an organic molecule that contains a certain amount of nitrogen atoms that is coordinated by all or some of said nitrogen atoms to manganese centers; z indicates the charge of the complex and is an integer that can be positive or negative; And it is a monovalent or multivalent counterion, which results in charge neutrality, which is dependent on the z-charge of the complex; and q = z / [load Y]

Preferred manganese complexes are those where x is CH ³ COO- or O ² , or mixtures thereof, most preferably where manganese is in the oxidation state IV and x is O2-. Preferred ligands are those that coordinate through three nitrogen atoms to one of the manganese centers, preferably being macrocyclic in nature. They are especially preferred:

(1) 1,4,7-trimethyl-1,4,7-triazacyclononane, (Me-TACN); Y

( ² ) 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, (Me-Me TACN).

The type of counterion Y to neutralize the charge is not decisive in terms of the activity of the complex and can be selected, for example, from any of the following counterions: chloride; sulfate; nitrate; methylsulfate; surfactant anions such as long chain alkyl sulfates, alkyl sulfonates, alkylbenzenesulfonates, tosylate, trifluoromethyl sulphonate, perchlorate (ClO ⁴ -), BPhY, and PFe - although some counterions are more preferred than others for reasons of product ownership and safety.

Accordingly, the preferred manganese complexes useful in the present invention are:

(I) [(Me-TACN) MnIV (Au-0) ³ MnIV (Me-TACN)] 2+ (PF ^{6-) 2}

(II) [(Me-MeTACN) MnIV (Ap-0) ³ MnIV (Me-MeTACN) r (PF ⁶ -) ²

(III) [(Me-TACN) MnIII (Au-0) (Ap-OAc) ² MnIII (Me-TACN)] 2+ (PF ⁶ -) ²

(IV) [(Me-MeTACN) MnIlI (Au-0) (Au-OAc) ² MnIII (Me-MeTACN)] 2+ (PF ⁶ -) ²

which in future can also be abbreviated as:

(I) [MnIV2 (Au-0) 3 (Me-TACN) 2] (P F ^

(II) [MnIV2 (Au-0) 3 (Me-MeTACN) 2] (PF ⁶ ) ²

(III) [MnIII2 (Au-0) (Au-OAc) ² (Me-TACN) ² ] (PF ⁶ ) ²

(IV) [MnIN2 (A | j-0) (A |> OAc) ² (Me-TACN) ² ] (PFe) ²

The structure of I is presented below:

abbreviated as [MnIV2 (A | -0) 3 (Me-TACN) 2] (PFa) ² -The structure of II is presented below:

abbreviated as [MnIV2 (A | -0) 3 (Me-MeTACN) 2] (PFa) ² -It should be noted that manganese complexes are also described in EP-A-0458397 and EP-A-0458398 as bleach catalysts and of unusually effective oxidation. In the following description of this invention they will also simply be called "catalyst."

Preferably the composition of the invention comprises from 0.001 to 1, more preferably from 0.002 to 0.01 grams of bleach catalyst. Preferably, the bleach catalyst is a manganese bleach catalyst.

Inorganic detergent builder

The composition of the invention preferably comprises an inorganic detergent builder additive. Suitable inorganic detergency builder additives are selected from the group consisting of carbonate, silicate and mixtures thereof. Sodium carbonate is especially preferred for use herein. Preferably the composition of the invention comprises from 1 to 8, more preferably from 2 to 6 and especially from 3 to 5 grams of calcium carbonate.

Surfactant

Surfactants suitable for use herein include non-ionic surfactants, preferably the compositions are free of other surfactants. Traditionally, non-ionic surfactants have been used in dishwashers for surface modification purposes, in particular for sagging to prevent the formation of films and fences, and to improve gloss. It has been discovered that non-ionic surfactants can also help prevent redeposition of dirt.

Preferably, the composition of the invention comprises a non-ionic surfactant or a non-ionic surfactant system, more preferably the non-ionic surfactant or the non-ionic surfactant system has a phase inversion temperature, measured at a concentration of 1% in distilled water, between 40 0C and 70 0C, preferably between 45 0C and 65 0C. By "non-ionic surfactant system" is meant herein a mixture of two or more non-ionic surfactants. Non-ionic surfactant systems are preferred for use herein. They appear to have improved cleaning and finishing properties, and better product stability than individual non-ionic surfactants.

The phase inversion temperature is the temperature below which a surfactant, or a mixture thereof, is preferably distributed in the aqueous phase as swollen micelles of oil, and above which it is preferably distributed in the oil phase. like water-swollen reverse micelles. The phase inversion temperature can be determined visually by identifying the temperature at which the turbidity appears.

The phase inversion temperature of a non-ionic surfactant or system can be determined as follows: a solution is prepared containing 1% of the corresponding surfactant or mixture by weight of the solution in distilled water. The solution is gently shaken before the phase inversion temperature analysis to ensure that the process is carried out in chemical equilibrium. The phase inversion temperature is taken in a thermostatic bath by immersing the solutions in 75 mm sealed glass test tubes. To ensure the absence of leaks, the test tube is weighed before and after the phase inversion temperature measurement. The temperature gradually increases at a rate below 10C per minute, until the temperature reaches a few degrees below the previously estimated phase inversion temperature. The phase inversion temperature is determined visually at the first indication of turbidity.

Suitable non-ionic surfactants include: i) ethoxylated non-ionic surfactants, prepared by reacting a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles especially preferred at least 16 moles, and even more preferred at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol; ii) alkoxylated alcohol surfactants having 6 to 20 carbon atoms and at least one ethoxy group and a propoxy group. For use herein, mixtures of surfactants i) and ii) are preferred.

Other suitable non-ionic surfactants are oxyalkylated polyalcohols terminally protected with epoxy groups represented by the formula:

R1 O [CH2CH (CH3) O] x [CH2CH2O] and [CH2CH (OH) R2] (I)

wherein R1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having 2 to 26 carbon atoms; x is an integer with an average value of 0.5 to 1.5 and more preferably about 1; e y is an integer with a value of at least 15, more preferably at least 20.

Preferably, the surfactant of Formula I has at least about 10 carbon atoms in the terminal epoxide unit [CH2CH (OH) R2]. Suitable formula I surfactants, according to the present invention, are the poly-TERGENT® SLF-18B non-ionic surfactants of Olin Corporation, such as those described, for example, in WO application 94/22800, filed October 13, 1994 by Olin Corporation.

Amine oxide type surfactants are useful in the composition of the invention. C10-C18 alkyl dimethylamine oxide, and C10-18 alkyl dimethylamine acyl oxide are preferred.

Surfactants may be present in amounts of 0.1 to 10, more preferably 0.5 to 5 and especially 0.8 to 3 grams.

Enzymes

For ease of reference, the following nomenclature will be used herein to describe the enzyme variants: Original amino acid (s): position (positions) of the substituted amino acid (s). IUPAC letter codes of standard enzyme for amino acids are used.

Proteases

Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline serine proteases, such as subtilisins (EC 3.4.21.62), as well as chemically or genetically modified mutants thereof. Suitable proteases include subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amiloliquefaciens, Bacillus pumilus and Bacillus gibsonii.

Especially preferred proteases for the detergent of the invention are polypeptides showing at least 90%, preferably at least 95%, more preferably at least 98%, even more preferably at least 99% and especially 100% identity with the natural enzyme from of Bacillus lentus, which comprise mutations in one or more, preferably in two or more, and more preferably in three or more of the following positions, using the BPN numbering system, and the amino acid abbreviations shown in WO00 / 37627, which are incorporated herein by reference: V68A, N87S, S99D, S99SD, S99A, S101G, S101M, S103A, V104N / I, G118V, G118R, S128L, P129Q, S130A, Y167A, R170S, A194 / V205I, V205I or V205I M222S

With maximum preference, the protease is selected from the group comprising the following mutations (BPN numbering system) against any of natural PB92 (seq. ID no .: 2 in WO 08/010925) or subtilisin 309 natural (sequence according to the main chain of PB92, except that it comprises a natural variation of N87S). (i) G118V S128L P129Q S130A

(ii) S101M G118V S128L P129Q S130A

(iii) N76D N87R G118R S128L P129Q S130A S188D N248R

(iv) N76D N87R G118R S128L P129Q S130A S188D V244R

(v) N76D N87R G118R S128L P129Q S130A

(vi) V68A N87S S101G V104N

Suitable commercial protease enzymes include those marketed under the trade names Savinase®, Polarzyme®, Kannase®, Ovozyme®, Everlase® and Esperase® from Novozymes A / S (Denmark), those marketed under the trade names Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase®, Ultimase® and Purafect OXP® from Genencor International, those marketed under the trade names Opticlean® and Optimase® from Solvay Enzyme, those marketed by Henkel / Kemira, especially BLAP

Preferred levels of protease in the product of the invention include from about 0.1 to about 10, more preferably from about 0.5 to about 7 and especially from about 1 to about 6 mg of active protease.

Amylases

The preferred enzyme for use herein includes alpha-amylases, including those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A preferred alkaline alpha-amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., Such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818) DSM 12368, DSMZ No. 12649, KSM AP1378 (WO 97/00324), KSM K36 or KSM K38 (EP 1,022,334). Preferred amylases include:

(a) the variants described in US-5,856,164 and WO99 / 23211, WO 96/23873, WO00 / 60060 and WO 06/002643, especially the variants with one or more substitutions at the following positions with respect to the AA560 enzyme listed as Sec. No. 12 in WO 06/002643:

9, 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 195, 202, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 320, 323, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 458, 461, 471, 482, 484, preferably also containing the deletions of D183 * and G184 *.

(b) variants that show at least 95% identity with the natural enzyme from Bacillus sp. 707 (seq. ID no .: 7 in US 6,093,562), especially those comprising one or more of the following mutations M202, M208, S255, R172, and / or M261. Preferably, said amylase comprises one of the M202L or M202T mutations.

Suitable commercial alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, POWERASE®, FUNGAMYL® and BAN® (Novozymes A / S, Bagsvaerd, Denmark), KEMZYM® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Vienna Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS® and PURASTAR OXAM® (Genencor International Inc ., Palo Alto, California) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). Especially preferred amylases for use herein include NATALASE®, STAINZYME®, STAINZYME PLUS®, POWERASE® and mixtures thereof.

Preferably, the product of the invention comprises at least 0.01 mg, preferably from about 0.05 to about 10, more preferably from about 0.1 to about 6, especially from about 0.2 to about 5 mg of active amylase.

Additional Enzymes

Additional enzymes suitable for use in the product of the invention may comprise one or more enzymes selected from the group comprising hemicellulases, cellulases, cellobiose dehydrogenases, peroxidases, proteases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannases, pectate lyases , keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pululanases, tannases, pentosanasas, malanases, B-glucanases, arabinosidases, hyaluronidase, chondroitinases, laccase, amylases, and mixtures thereof. Preferably, the protease and / or amylase of the product of the invention are in the form of granules, the granules comprise less than 29% sodium sulfate by weight of the granulate or sodium sulfate and the active enzyme (protease and / or amylase) They are in a weight ratio of less than 4: 1.

Crystal Growth Inhibitor

Crystal growth inhibitors are materials that can bind calcium carbonate crystals and prevent further growth of species such as aragonite and calcite.

An especially preferred crystalline growth inhibitor for use herein is HEDP (1-hydroxyethylidene-1,1-diphosphonic acid). Preferably, the composition of the invention comprises 0.01 to 1, more preferably 0.05 to 0.8 grams of a crystalline growth inhibitor, preferably HEDP. Agents for the care of metals

Metal care agents can prevent or reduce tarnish, corrosion or oxidation of metals, including aluminum, stainless steel and non-ferrous metals, such as silver and copper. Preferably, the composition of the invention comprises from 0.001 to 0.01, more preferably from 0.002 to about 0.009 grams; preferably, the metal care agent is benzotriazole (BTA).

Agents for glass care

Glass care agents protect the appearance of glassware during the dishwashing process. Preferably, the composition of the invention comprises 0.001 to 1, more preferably 0.002 to 0.5 grams of a glass care agent; preferably the glass care agent is a zinc salt. Examples

Two bags of two compartments for dishwashers were made comprising the ingredients hereinbelow (Composition 1 (comparative) and Composition 2 (according to the invention)). The bags were made of polyvinyl alcohol (Monosol 8630 marketed by Kuraray) with solid and liquid components in different compartments.

MGDA Trisodium salt of diacetic methylglycine acid.

Stainzyme plus x® amylase marketed by Novozymes

Ultimase® protease marketed by DuPont

TAED bleach activator (Tetraacetylethylenediamine)

Bleach Catalyst Manganese Bleach Catalyst

HEDP 1-Hydroxyethylidene-1,1,1-diphosphonic acid

Plurafac SLF-180 Non-ionic surfactant supplied by BASF

Lutensol TO7 Non-ionic surfactant supplied by BASF

RA Reserve Alkalinity

Tea stain removal test

Eight cups were poured per test group using black tea (Assam) prepared in artificially hard water with ferric sulfate according to the IKW test method (dishwashing detergents of the IKW working group. “Methods for Ascertaining the Cleaning Performance of Dishwasher Detergents (Part B, updated in 2005). ”SOFW-Journal, 132, 8-2006 pages.

35). For each composition, two cups were placed on the top shelf of a dishwasher, loaded with loading plates, and washed using Compositions 1 and 2. The inlet water had a hardness of 360 ppm CaCO ³ .

As an artificial load, 100 g of IKW dirt and 36 g of minced meat from frozen were added. The IKW artificial dirt was prepared according to the IKW procedure and the meat dirt was prepared by mixing 225 g of minced meat (50% pork and 50% veal), 75 g of eggs (white and yolk) and 80 g of water (hardness 350 ppm of CaCOs), and mixed to form a paste, then divided into containers containing 36 g of the ground beef paste and stored in a freezer.

The test was carried out in a Miele GSL dishwasher with a normal cycle of R-50 0C (without prewash). The detergent is added to the dishwasher when the dispenser door is opened. The rehearsal was repeated three more times with the rest of the cups, once all were washed, the eight cups were classified by three independent judges, using a visual scale of 1 to 10 ranging from dirty to completely clean.

Composition 2, according to the invention, provides much better cleaning of the tea than Composition 1, outside the scope of the invention.

Film and stain formation tests in multiple cycles

A “Test of the effectiveness of rinsing and prevention of calcareous residues” was carried out in (1140 Rue Andre Ampere, 13851 Aix-en-Provence, France); The trial consisted of evaluating the rinse capacity and the prevention of calcareous residues of the product, that is, leaving the dishes washed with the least possible spots, streaks and film formation, restoring their initial brightness. Test conditions: 30 wash cycles at 55 ° C, Universal cycle in Miele dishwasher -, water hardness 350 ppm of CaCO ³ . Artificial IKS dirt (according to the IKW method) was introduced at the beginning of each cycle, to reproduce a cycle in stained conditions.

Different materials were used that represent what is usually washed in a dishwasher: ceramic plates, glasses, plastics, stainless steel cutlery. The materials were assessed visually with two types of daytime running lights to detect serious anomalies and with more intense artificial light to detect minor faults. Each article was examined under the two types of lights and scored according to the following scales:

• Movie: from 1 to 4 (1 is considerably movie and 4 without movie at all)

• Stains and streaks: from 0 to 8 (0 is considerably stained and 8 there are no stains at all)

The evaluation of the film formation was carried out after thirty washing cycles, while the evaluation of the formation of spots was carried out only after five cycles because beyond this number of cycles, the film deposits alter and inhibit the development of spots.

Compositions 1 and 2 showed an equivalent performance of film formation. Composition 2, according to the invention, indicates a better ability to prevent stains. This was surprising given that the level of polymer was considerably lower in the composition of the invention than in the comparative composition

Cleaning tests

Compositions 1 and 2 were also compared according to their cleaning capacity using CFT tiles, (Center For Testmaterials BV. Stoomloggerweg 11, 3133 KT Vlaardingen, Netherlands), which are monitors for stained melamine dishwashers that discriminate product performance to remove stains sensitive to enzymes among others.

Two tiles are placed by washing each stain on the top shelf of a Miele 1022 dishwasher, adding an additional 50 g of frozen IKW load at the beginning of the wash. The inlet water had a water hardness of 376 ppm of CaCO ³ and the cycle used was R-50 0C a (without prewash). The test was repeated three more times using new tiles each time. In the end, the tiles were evaluated using a computer-assisted image analysis to assign a stain removal rate, which has a continuous scale of 0 to 100, where 0% is unwashed or 100% is a complete stain removal .

Composition 2, according to the invention, provides a better protein withdrawal than Comparative Composition 1.

Claims (14)

1. A phosphate-free dishwashing detergent composition in the form of a unit dose having a weight of 8 to 25 grams, the composition comprising: i) more than 5 to 8 grams of an organic complexing agent selected from the group consisting of methylglycinadiacetic acid, its salts and derivatives thereof, N, N-diaceticglutamic acid, its salts and derivatives thereof, iminodisuccinic acid, its salts and derivatives thereof, carboxymethylinulin, its salts and derivatives thereof, and mixtures thereof; ii) a dispersing polymer; iii) 1 to 3 grams of bleach and wherein the complexing agent and the dispersing polymer are in a weight ratio of 10: 1 to 20: 1. 2. A composition according to the preceding claim wherein the complexing agent is selected from the group consisting of methylglycinadiacetic acid, its salts and derivatives thereof, preferably the trisodium salt of methylglycinadiacetic acid. 3. A composition according to any of the preceding claims wherein the dispersing polymer is selected from the group consisting of polycarboxylated polymers, sulfonated polymers and mixtures thereof, preferably a sulfonated polymer. 4. A composition according to any of the preceding claims wherein the composition is practically free of citrate. 5. A composition according to any of the preceding claims which further comprises an enzyme selected from amylase, protease and a mixture thereof. 6. A composition according to any of the preceding claims which further comprises 0.05 to 0.8 grams of a crystalline growth inhibitor, preferably 1-hydroxyethylidene-1,1-diphosphonic acid. 7. A composition according to any of the preceding claims which further comprises a manganese bleach catalyst. 8. A composition according to any of the preceding claims wherein i) the complexing agent is a salt of the methylglycinadiacetic acid; ii) the dispersing polymer is a sulfonated polymer; Y iii) the bleach is sodium percarbonate. 9. A composition according to the preceding claim comprising i) 5.5 to 7 grams of the salt of the methylglycinadiacetic acid; ii) 1 to 3 grams of sodium percarbonate; Y wherein the salt of the methylglycinadiacetic acid and the sulfonated polymer are in a weight ratio of 10: 1 to 20: 1. 10. A composition according to any one of the preceding claims having a pH equal to or greater than 9 to 12 as measured in a 1% by weight / volume aqueous solution at 20 ° C. 11. A composition according to any one of the preceding claims having a reserve alkalinity equal to or greater than 10 to 20 at a pH of 9.5 measured in NaOH with 100 ml of product at 20 ° C. 12. A method of washing the dishes in a dishwasher comprising the step of subjecting the dishes to a washing solution comprising a composition according to any of the preceding claims. 13. A method for washing the dishes in a dishwasher according to the previous claim wherein the cleaning is produced using hard water having a hardness equal to or greater than 100 ppm of CaCO ³ . 14. Use of a composition according to any one of claims 1 to 11 for the removal of stains containing protein in a dishwasher using hard water having a hardness equal to or greater than 100 ppm of CaCO ³ .